CN105566684A - Method for preparing microcapsule-coated ammonium polyphosphate through in-situ polymerization molecular self-assembly - Google Patents
Method for preparing microcapsule-coated ammonium polyphosphate through in-situ polymerization molecular self-assembly Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
- C08G12/30—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds with substituted triazines
- C08G12/32—Melamines
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/322—Ammonium phosphate
- C08K2003/323—Ammonium polyphosphate
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Abstract
The invention discloses a method for preparing microcapsule-coated ammonium polyphosphate through in-situ polymerization molecular self-assembly. The method includes mixing formalin with melamine, increasing the temperature for condensation reaction after adjusting pH value of the mixture to 8-9, lowering the temperature after reaction, adding water and ammonium polyphosphate, stirring the mixture for 1-2 hours, adding cyanuric acid, increasing the temperature for in-situ polymerization reaction, coating the ammonium polyphosphate with a microcapsule, and performing filtering and drying after reaction to obtain the microcapsule-coated ammonium polyphosphate. The method has the advantages that the technological operation process is simple, ammonium polyphosphate coating rate is high, water solubility of the ammonium polyphosphate is reduced greatly, high dispersity and compatibility of the ammonium polyphosphate and polymer materials are achieved after coating, and flame retarding effect is remarkable; moreover, adhesion of the ammonium polyphosphate and resin to the inner wall of a reaction kettle is avoided during reaction, the reaction kettle is easy to clean, raw material utilization rate is increased and heat transfer efficiency of the reaction kettle is improved.
Description
Technical field
The present invention relates to a kind of micro encapsulation method for coating of ammonium polyphosphate, be specifically related to a kind of method being prepared microcapsule-coated ammonium polyphosphate by in-situ polymerization numerator self-assembly technique, belong to field of material technology.
Background technology
Expanding halide-free fire-retardant has the advantages such as Flame-retardant low-smoke, low toxicity, corrosion-free air release, is halogen-free flame retardants most with prospects, is described as the revolution in flame-retarded technology, becomes the focus of recent domestic research.Ammonium polyphosphate is as one of the main component of expansion type flame retardant, because its phosphorus content is high, nitrogen content large, Heat stability is good, have simultaneously low price, toxicity lower, use the advantages such as comparatively safe, be widely used as the fire-retardant of coating, plastics, fiber, rubber etc.But ammonium polyphosphate is due to the chemical structure of himself, water absorbability is very strong, easily reunites, and with the poor compatibility of polymer materials, very easily oozes out to material surface migration, reduce the comprehensive effectiveness especially flame retardant properties of material when high temperature, high humidity.The polymerization degree of ammonium polyphosphate is higher, water-soluble less, although the water-soluble of high polymerization degree APP obtains remarkable improvement, and still can because of lost effective constituents such as hydrolysis when temperature is higher.
In order to reduce the water-soluble of ammonium polyphosphate, improving thermostability, improving the consistency with polymer base material, suitable modification can be carried out to ammonium polyphosphate surface.Comparatively common ammonium polyphosphate modification technology mainly contains coupling agent modified technology, surfactant-modified technology, cyanurotriamide modified technology and microcapsule coated technology etc. at present.Wherein, with silane coupling agent to ammonium polyphosphate modifying surface, test result shows, modified ammonium polyphosphate particle surface is hydrophobicity, dispersiveness in resin is greatly improved, but because the price of silane coupling agent own is higher and preparation technology is more complicated, be not suitable for extensive industrialization.After utilizing tensio-active agent process ammonium polyphosphate particles surface, consistency and the dispersiveness of ammonium polyphosphate and organic resin can be improved, but its water absorbability can not be improved.Utilizing trimeric cyanamide to carry out surface modification is also the many problem of Recent study, more commonly by a certain amount of trimeric cyanamide and ammonium polyphosphate Hybrid Heating, trimeric cyanamide is coated on the surface of ammonium polyphosphate, but trimeric cyanamide itself is polarity, still there is hygroscopicity problems.
Microcapsule coated technology is that research is more at present, a kind of technology that application surface is the widest.More external companies such as commercialized product such as a gram Lay benefactor department, Monsanto Company and Hoechst AG are micro encapsulation ammonium polyphosphate product.Patent EP3531500 terpolycyantoamino-formaldehyde resin micro encapsulation prepares melmac coated ammonium polyphosphate; Patent US5321027 and US5576391 uses aminoresin micro encapsulation coated ammonium polyphosphate in formaldehyde solution; Adopt the method disclosed in above patent carry out micro encapsulation coated time, ubiquity clad ratio is wayward, coated incomplete problem.Patent DE2949537, DE3005252 and DE3316880 disclose with melamine-formaldehyde resin or phenol-formaldehyde resin is coated, preparation has resistant to hydrolysis performance, the method for the ammonium polyphosphate powder of excellent in stability.Compared with the ammonium polyphosphate without microcapsule coated process, the water-soluble obvious reduction of ammonium polyphosphate after coated, thermostability improves, but, when adopting the method disclosed in above patent to carry out microcapsule coated process, reactor inwall there will be the knot wall phenomenon of a large amount of ammonium polyphosphate and resin, and deteriorative reaction still conducts heat.In addition, adopt the microcapsule-coated ammonium polyphosphate that these class methods obtain, particle diameter is obviously thicker, even has block to be formed, needs pulverization process during use, causes breaking of microcapsule, and stability declines.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of method that in-situ polymerization molecular self-assembling prepares microcapsule-coated ammonium polyphosphate, the method reacts the polymkeric substance of formation for wall material with trimeric cyanamide, formaldehyde and cyanuric acid, microcapsule coated is carried out to ammonium polyphosphate, mild condition, flow process are simple, are convenient to suitability for industrialized production.
The present invention take ammonium polyphosphate as capsule-core, with trimeric cyanamide, formaldehyde and cyanuric acid are polymerization single polymerization monomer, microcapsule-coated ammonium polyphosphate is prepared by in-situ polymerization numerator self-assembly technique in aqueous phase system, in the microcapsule formed, ammonium polyphosphate is capsule-core, trimeric cyanamide, the polymkeric substance that formaldehyde and cyanuric acid reaction are formed is wall material, also cyst wall can be referred to as, the raw materials used safety of the method, be easy to get, technical operation flow is simple, reaction conditions is gentle, high to the clad ratio of ammonium polyphosphate, the stability of ammonium polyphosphate can be improved, reduce its water-soluble, improve the consistency of itself and polymer base material.
In the present invention, described in-situ polymerization numerator self-assembly technique refers to: trimeric cyanamide, formaldehyde and cyanuric acid polymerization reaction take place in system, and the polymkeric substance that reaction generates is at the surface self-organization of ammonium polyphosphate, and ammonium polyphosphate is coated, forms microcapsule.The ammonium polyphosphate modified by this technology has good stability, and water-soluble is low, with the advantage such as the consistency of polymer base material is better.
The concrete technical scheme of the present invention is as follows:
In-situ polymerization molecular self-assembling prepares a method for microcapsule-coated ammonium polyphosphate, and the method comprises the following steps:
(1) by formalin and trimeric cyanamide mixing, adjustment mixture pH heats up after 8-9 to carry out condensation reaction;
(2) cooling after reaction, then add water and ammonium polyphosphate, stir 1-2h, then add cyanuric acid, heat up and carry out home position polymerization reaction, microcapsule coated is carried out to ammonium polyphosphate, filter after reaction, dry, obtain microcapsule-coated ammonium polyphosphate.
In above-mentioned preparation method, formaldehyde adds in form of an aqueous solutions, and formalin can use the formalin of 35-37% conventional on market.
In above-mentioned preparation method, when formalin concentration is 37%, the mass ratio of trimeric cyanamide, formalin and ammonium polyphosphate is 1:1-2:4-6, preferred 1:1.5:5.Adopt preferred mass than time, the performance of products obtained therefrom is better.
In above-mentioned steps (1), formaldehyde and trimeric cyanamide react at 65-75 DEG C.General, the reaction times is 0.5-1h.After reaction, obtain clear soln.
In above-mentioned steps (1), pH can be regulated with sodium bicarbonate.
In above-mentioned steps (2), after adding water, ammonium polyphosphate and cyanuric acid, mixed system carries out home position polymerization reaction, carries out coated to ammonium polyphosphate.The ammonium polyphosphate added and the mass ratio of water are 1:3-5, preferred 1:3.3.Water herein, refers to the pure water added in step (2).
In above-mentioned steps (2), the weight ratio of cyanuric acid and ammonium polyphosphate is 1:4-6, preferred 1:5.When adopting preferred weight ratio, the performance of products obtained therefrom is better.
In above-mentioned preparation method, step (1) is reacted at relatively high temperatures, and after reaction, cooling adds water and ammonium polyphosphate again.In the specific embodiment of the invention, be cooled to 25-35 DEG C and then add water and ammonium polyphosphate.
In above-mentioned steps (2), be warming up to 40-100 DEG C after adding cyanuric acid and carry out home position polymerization reaction, preferred 40-80 DEG C.
In above-mentioned steps (2), after adding cyanuric acid, reaction 3-4h.
Polymerization degree n >=1000 of the ammonium polyphosphate that the present invention is used.The polymkeric substance that the polymerization of trimeric cyanamide, formaldehyde and cyanuric acid is formed carries out coated as cyst material to ammonium polyphosphate.This polymkeric substance is also a kind of resin, and as shown in Figure 1, each monomer constantly carries out connecting, being polymerized according to this rule its structural formula schematic diagram.This resin viscosity that trimeric cyanamide, formaldehyde and cyanuric acid are formed is little, is easy to stir when carrying out coated to ammonium polyphosphate, and trimeric cyanamide is uniformly dispersed, and completely coated, clad ratio is high.The microcapsule-coated ammonium polyphosphate formed have good stability, water-soluble low, with the advantage such as the consistency of polymer base material is better.
The present invention has the following advantages:
1, the inventive method take ammonium polyphosphate as capsule-core, trimeric cyanamide, formaldehyde and cyanuric acid are polymerization single polymerization monomer, microcapsule-coated ammonium polyphosphate is prepared by numerator self-assembly technique in aqueous systems, raw materials used safely, be easy to get, reaction conditions is gentle, and technical operation flow is simple, and the ammonium polyphosphate after coated discharges without free formaldehyde, safety and environmental protection, is convenient to suitability for industrialized production.
2, the inventive method ammonium polyphosphate clad ratio is high, greatly reduce the water-soluble of ammonium polyphosphate, relative ammonium polyphosphate simultaneously, its surface polarity reduces greatly, with polymer materials, there is better dispersed and consistency, solve solubleness in ammonium polyphosphate water comparatively large, poor with polymeric matrix compatible, be difficult to the technical barrier meeting fire retardant material application requiring in wet environment.
3, adopt the inventive method gained microcapsule-coated ammonium polyphosphate thermostability strong, particle diameter does not obviously become greatly, caking of not easily reuniting, and can directly use without the need to pulverizing, avoid pulverize cause microcapsules rupture, stability reduction problem.
4, the cyst wall of microcapsule of the present invention and capsule-core have fire-retardant synergy, and compared with not coated ammonium polyphosphate, flame retardant effect significantly improves.
5, to be polymerized the black check wall material viscosity obtained little for trimeric cyanamide of the present invention, formaldehyde and cyanuric acid, good fluidity, in reaction process, reactor inwall is without the knot wall phenomenon of ammonium polyphosphate and resin, is easy to cleaning, improves the utilization ratio of raw material and the heat transfer efficiency of reactor.
Accompanying drawing explanation
The structural formula schematic diagram of the polymkeric substance that Fig. 1 trimeric cyanamide, formaldehyde and cyanuric acid are formed.
Embodiment
Below in conjunction with specific embodiment, the present invention is further described, so that those skilled in the art more understands the present invention, but does not therefore limit the present invention.
In following embodiment, all raw materials all commercially can be bought and obtain, and wherein the polymerization degree of ammonium polyphosphate used is n >=1000.
In following embodiment, described formaldehyde all refers to the formalin of mass concentration 37%.
embodiment 1
With in the 2L reactor of agitator, thermometer and condensation reflux unit, add 45g trimeric cyanamide and 45g formaldehyde (37wt% formalin, lower same), regulate pH to be 8-9 with sodium bicarbonate, be warming up to 70 DEG C of reaction 0.5-1h, be cooled to 30 DEG C after reaction, then add 180g ammonium polyphosphate and 540g deionized water, stir 1-2h, add 45g cyanuric acid again, rise to 40 DEG C of stirring reaction 3-4h, filter after reaction, dry, obtain 268g molecular self-assembling microcapsule-coated ammonium polyphosphate.
embodiment 2
With in the 2L reactor of agitator, thermometer and condensation reflux unit, add 36g trimeric cyanamide and 36g formaldehyde, adjustment pH is 8-9, is warming up to 70 DEG C of reaction 0.5-1h, is cooled to 30 DEG C after reaction, then 180g ammonium polyphosphate and 720g deionized water is added, stir 1-2h, then add 36g cyanuric acid, be warming up to 60 DEG C of stirring reaction 3-4h, filter after reaction, dry, obtain 248.6g molecular self-assembling microcapsule-coated ammonium polyphosphate.
embodiment 3
In the reactor of the 2L with agitator, thermometer and condensation reflux unit, add 30g trimeric cyanamide and 30g formaldehyde, adjustment pH is 8-9, is warming up to 70 DEG C of reaction 0.5-1h, is cooled to 30 DEG C after reaction, then 180g ammonium polyphosphate and 900g deionized water is added, stir 1-2h, then add 30g cyanuric acid, be warming up to 60 DEG C of stirring reaction 3-4h, filter after reaction, dry, obtain 233.6g molecular self-assembling microcapsule-coated ammonium polyphosphate.
embodiment 4
With in the 2L reactor of agitator, thermometer and condensation reflux unit, add 36g trimeric cyanamide and 54g formaldehyde, adjustment pH is 8-9, is warming up to 70 DEG C of reaction 0.5-1h, is cooled to 30 DEG C after reaction, then 180g ammonium polyphosphate and 594g deionized water is added, stir 1-2h, then add 36g cyanuric acid, be warming up to 80 DEG C of stirring reaction 3-4h, filter after reaction, dry, obtain 245.2g molecular self-assembling microcapsule-coated ammonium polyphosphate.
embodiment 5
With in the 2L reactor of agitator, thermometer and condensation reflux unit, add 30g trimeric cyanamide and 36g formaldehyde, adjustment pH is 8-9, is warming up to 75 DEG C of reaction 0.5-1h, is cooled to 30 DEG C after reaction, then 180g ammonium polyphosphate and 594g deionized water is added, stir 1-2h, then add 36g cyanuric acid, be warming up to 80 DEG C of stirring reaction 3-4h, filter after reaction, dry, obtain 238.3g molecular self-assembling microcapsule-coated ammonium polyphosphate.
embodiment 6
With in the 2L reactor of agitator, thermometer and condensation reflux unit, add 30g trimeric cyanamide and 60g formaldehyde, adjustment pH is 8-9, is warming up to 70 DEG C of reaction 0.5-1h, is cooled to 30 DEG C after reaction, then 180g ammonium polyphosphate and 594g deionized water is added, stir 1-2h, then add 36g cyanuric acid, be warming up to 80 DEG C of stirring reaction 3-4h, filter after reaction, dry, obtain 242.6g molecular self-assembling microcapsule-coated ammonium polyphosphate.
embodiment 7
With in the 2L reactor of agitator, thermometer and condensation reflux unit, add 36g trimeric cyanamide and 72g formaldehyde, adjustment pH is 8-9, is warming up to 70 DEG C of reaction 0.5-1h, is cooled to 30 DEG C after reaction, then 180g ammonium polyphosphate and 594g deionized water is added, stir 1-2h, then add 36g cyanuric acid, be warming up to 80 DEG C of stirring reaction 3-4h, filter after reaction, dry, obtain 253.3g molecular self-assembling microcapsule-coated ammonium polyphosphate.
embodiment 8
With in the 2L reactor of agitator, thermometer and condensation reflux unit, add 30g trimeric cyanamide and 30g formaldehyde, adjustment pH is 8-9, is warming up to 65 DEG C of reaction 0.5-1h, is cooled to 35 DEG C after reaction, then 180g ammonium polyphosphate and 594g deionized water is added, stir 1-2h, then add 30g cyanuric acid, be warming up to 100 DEG C of stirring reaction 3-4h, filter after reaction, dry, obtain 234.8g molecular self-assembling microcapsule-coated ammonium polyphosphate.
In above-described embodiment 1-8, after adding cyanuric acid, mixed solution is easy to stir, and viscosity is little, adheres to, reactor inner clean after reaction on reactor inwall without ammonium polyphosphate and resin, and the product cut size after oven dry does not obviously become large, and soilless sticking caking phenomenon, need not pulverize.
comparative example 1
With in the 2L reactor of agitator, thermometer and condensation reflux unit, add 36g trimeric cyanamide and 54g formaldehyde, adjustment pH is 8-9, be warming up to 70 DEG C of reaction 0.5-1h, be cooled to 30 DEG C after reaction, then add 180g ammonium polyphosphate and 594g deionized water, stir 1-2h, be warming up to 80 DEG C of stirring reaction 3-4h, filter after reaction, dry, obtain 224.7g molecular self-assembling microcapsule-coated ammonium polyphosphate.
comparative example 2
With in the 2L reactor of agitator, thermometer and condensation reflux unit, add 36g trimeric cyanamide, then add 180g ammonium polyphosphate and 594g deionized water, stir 1-2h, then add 36g cyanuric acid, be warming up to 80 DEG C of stirrings to react, after intensification, system viscosity sharply rises, and is difficult to stir, reactor inwall has large quantity of material to adhere to, and cannot carry out subsequent step.
below, following performance test is carried out to the product that embodiment and comparative example obtain.
, ammonium polyphosphate coated front and back particle diameter, changes in solubility situation:
1.1 product granularities adopt Beckman company of U.S. laser particle size analyzer to analyze, model LS230.
1.2 solubleness testing method: accurately take 10 grams of microcapsule-coated ammonium polyphosphates and be placed in 100ml deionized water, stir 1 hour at 25 DEG C, centrifugal settling, get supernatant liquor 50ml, heating dewaters and is dried to constant weight, be weighed as W gram, the solubleness of derived sample at 25 DEG C is 2W (g/100ml water).
, flame retardant effect test:
Molecular self-assembling microcapsule coated and not coated ammonium polyphosphate are added in polypropylene, makes anti-flaming polypropylene material, respectively vertical combustion is carried out to them and test coated front and back flame retardant effect.
The preparation method of anti-flaming polypropylene material: by molecular self-assembling microcapsule coated or not coated ammonium polyphosphate and polypropylene by 25:75 weight ratio on the twin screw extruder 180 DEG C extrude, dried pellet of extruding is injected sample batten (size of sample: 120mm × 13mm × 3.2mm) on injection moulding machine.
Sample batten is carried out vertical combustion rank test, tests according to UL94-2013 standard test methods test, the results are shown in following table 2.
Claims (10)
1. in-situ polymerization molecular self-assembling prepares a method for microcapsule-coated ammonium polyphosphate, it is characterized in that comprising the following steps:
(1) by formalin and trimeric cyanamide mixing, adjustment mixture pH heats up after 8-9 to carry out condensation reaction;
(2) cooling after reaction, then add water and ammonium polyphosphate, stir 1-2h, then add cyanuric acid, heat up and carry out home position polymerization reaction, microcapsule coated is carried out to ammonium polyphosphate, filter after reaction, dry, obtain microcapsule-coated ammonium polyphosphate.
2. preparation method according to claim 1, is characterized in that: when formalin concentration is 37%, and the mass ratio of trimeric cyanamide, formalin and ammonium polyphosphate is 1:1-2:4-6, is preferably 1:1.5:5.
3. preparation method according to claim 1, is characterized in that: polymerization degree n >=1000 of ammonium polyphosphate.
4. the preparation method according to claim 1,2 or 3, is characterized in that: in step (2), and the ammonium polyphosphate added is 1:3-5 with the mass ratio of the water added, preferred 1:3.3.
5. the preparation method according to claim 1,2 or 3, is characterized in that: the weight ratio of cyanuric acid and ammonium polyphosphate is 1:4-6, preferred 1:5.
6. preparation method according to claim 1, is characterized in that: in step (1), and formaldehyde and trimeric cyanamide react at 65-75 DEG C.
7. the preparation method according to claim 1 or 6, is characterized in that: in step (1), and the reaction times is 0.5-1h.
8. preparation method according to claim 1, is characterized in that: in step (2), be cooled to 25-35 DEG C after reaction, and then add water and ammonium polyphosphate.
9. preparation method according to claim 1, is characterized in that: in step (2), is warming up to 40-100 DEG C and reacts, preferred 40-80 DEG C after adding cyanuric acid.
10. the preparation method according to claim 1 or 9, is characterized in that: in step (2), after adding cyanuric acid, reaction 3-4h.
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| CN112940475A (en) * | 2021-02-05 | 2021-06-11 | 合肥工业大学 | Flame-retardant composite material and preparation method thereof |
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